Lubrication



Patented June 7, 1938 UNITED STATES LUBRIOATION Carl F. Prutton, East Cleveland, om, a'ssignor,

by mesne assignments, to The Lubri-Zoi Development Corporation, Cleveland, Ohio,

v poration of Delaware No Drawing.

6Claims.

This invention relates, as indicated, to improved lubricating compositions and more specifically to a new and improved addition agent for lubricating compositions generally; the methv od-of producing such addition agent and the new and improved lubricating compositions resulting from the use of such addition agent.

In recent years there has been an increasing demand for improved'lubricating compositions 10 having improved characteristics which are not possessed by the usual plain mineral lubricating oils. Among the improved properties thus desired are extreme pressure characteristics, im- 1 proved cold test, freedom from sludge, etc.

have been suggested for use as additions to lubricating compositions may be generally divided into two principal classes, 1. e., compounds which have been very carefully chemically isolated,

for use under substantially allconditions and will not hydrolizeand cause" destructive" corrosion even when subjected to high temperatures in the presence of substantial amounts. of moisture;

The second class of halogenated organic compounds which have been employed are the halogenated complex petroleum derivatives whose principal appeal has been their low cost. Compounds falling within the last-named class, while admirably suited to provide extreme pressure lubricants for gears and the like are, however, unsuited for use in lubricants to be employed in the crankcases of internal combustion engines due to the fact that heretofore'such materials have contained objectionable amounts of relativelyunstable constituents.

A halogenated addition agent which is rather complex in its chemical structure, i. e., contains a rather wide variety of individual compounds, has, however, certain very desirable characteristics when used as an addition agent in that the wide variety of compounds present makes possible the securing of desired results of the various types previously enumerated and over 'a wide range of operating conditions such as temperature and pressure.

It is the principal object of my invention to provide an addition agent for lubricating compositions which ls of a chemically complex nature and which has, however, been so stabilized that its use is now possible under certain types of conditions under which similar-complex materials of the-prior art were entirely unsuited, principally on account of their instability.

The halogenated organic compounds which treated and stabilized, so that they are suitable a cor- Application November 16, 1938, Serial No. 111,111

It is a further object of my invention to provide a method of producingthe complex addition agent previously defined, which method is characterized by its simplicity and low cost of operation, so that the resultant addition agent is made available at relatively low cost.

It is a further object of my invention to provide an improved lubricating composition having as its principal constituent my improved halogenated complex addition agent.

Other objects of my invention will appear as the description proceeds.- To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described, and particularly' pointed out in the claims, the following description setting forth in detail "one approved combination of ingredients embodying my invention, such disclosed means constitutin however, but one of various forms in whichthe principle of the invention may be used.

This invention may be broadly stated as comprising the discovery that a new and improved stabilized halogenated complex organic addition agent for lubricating compositions may be satisfactorily and economically produced and that lubricating compositions containing the same have unexpected desirable properties.

The process of producing my improved addition agent may be briefly described as follows:- Any complex or heterogeneous mixture of organic compounds such as are found in mineral oil, mineral oil fractions such as scale wax, paraffin wax, etc., coal tar and wood distillates, is halogenated by the usual procedure well known to those familiar with the art until the composition contains from about 10% to about of halogen.

The product immediately resulting from the halogenation step may be subjected to any of the well-known methods of removing the excess halogen, as well as certain of the more unstable of the halogen compounds, such processes comprising air blowing, treatment with an alkali, etc. The product resulting from this preliminary stabilizing step will be found to contain various quantities of halogenated aromatic or aliphatic compounds, or both. In case both types of compounds are present the proportional relationship between the same will, of course, depend upon the composition of the starting material, the degree of halogenation and the particular preliminary stabilizing process such as air blowing or alkali treatment which has been employed.

Certain of the halogenated compounds present in this resultant heterogeneous mixtitre of halogenated constituents are, however, 0 unstable that while the composition may be admirably suited as an extreme pressure addition agent to lubricants useful in gear cases and the like, nevertheless such compounds are too unstable to permit their safe use under conditions such as those encountered in crankcases or internal combustion engines.

The composition containing a heterogeneous mixtureof halogenated compounds prepared in the previously described or any other conventional process, is next heated with anhydrous aluminum chloride or equivalent agent according to conventional practice in the well-known Friedel- Crafts or similar condensation reaction during which the more unstable of the halogenated com-' pounds react with one another, or with other compounds present in the composition. During the reaction, the less stable halogenated compounds,'-if aliphatic, may become attached as aly present.

. This treatment with an agent such as AlCl: is most eflicient in causing the condensation of halogenated aromatic with halogenated aliphatic compounds but is also more or less effective in causing the'condensation of halogenated cyclic compounds (as typified by halogenated cyclohexane) with halogenated'aliphatic compounds, and

halogenated aliphatic compounds with other halogenated aliphatic compounds; Since the condensation is most emcient when occurring between halogenated aromatic and halogenated aliphatic compounds, it may, on occasion, be desirable to add up to about 20% of halogenated aromatic compounds to insure the combination of substantially all of the relatively unstable halogenated aliphatic constituents.

The aluminous sludge resulting from the Friedel-Crafts reaction is then removed according to conventional practice, such as by diluting the mixture with a light hydrocarbon solvent to promote settling and then distilling off the solvent.

The resultant composition which comprises the new composition of matter aocordingto my invention, will, when the starting material has been a petroleum derivative, contain minor amounts of more or less halogenated alkylated aromatic compounds and their derivatives and major proportions of relatively stable halogenated aliphatic compounds.

Inasmuch as the addition agent thus prepared is to be used most generally ina mineral lubricating oil or grease, a certain amount of care ,should be exercised inselecting the starting material so that the resultantcomposition, after halogenation and after the Friedel-Crafts reaction, will be soluble in or miscible with mineral oil and have a suil'lciently high boiling point or low vapor pressure that it will not be volatilized at the temperatures encountered during its contemplated use. 13hr example, the resultant composition to be used as an addition agent should have a vapor pressure less than atmospheric at a temperature of 140.and preferably at a temperature of 170.

If certain of the addition agents thus prepared are found to be of such a heavy consistency as not to be readily dissolved in or miscible with mineral oil, a mutual solvent may be employed for the purpose of facilitating the preparation of the final composition.

The new addition agent prepared in accordance with the process which comprises one of the phases of this invention may be added to any suitable lubricating composition base, the one most generally used being mineral lubricating oil. When mineral lubricating oil is used as the base, my new and improved addition agent may be "added to the mineral oil base in various percentages from about .1% to about 20% depending upon the particular use for which the final composition is designed. For use under conditions where high temperatures and extreme pressures are encountered, such as in crankcase lubricants,

from about .1% to about 10%; and. preferably from about 25% to about 3.5% of the addition agents may be added to mineral oil. It is also within the contemplation of my invention to employ my improved addition agent in conjunction with certain other oils which may be generally classified as non-mineral oils and which include animal oils, vegetable oils, etc usedv either asthe lubricating oil base or likewise as 'an addition agent to a mineral lubricating oil base.

My new and improved addition agent, when added to lubricating oil bases of the character previously described, will be found to desirably improve theextreme pressure characteristics of the resultant composition, lower the cold test of such composition, and generally improve the sludging characteristics of the composition. All

of the halogen compounds present in the heterogeneous mixture are more or less effective in aflfording extreme pressure characteristics. Halogenated alkylated aromatic compounds 'in the heterogeneous mixture are particularly effective to improve the cold test of the lubricating composition since only. small percentages of such compounds are usually required in order to markedly improve this property of a mineral lubricating oil. The presence of a wide variety of halogenated compounds in the heterogeneous mixture is, particularly advantageous in that the improved properties of the lubricating composition containing such heterogeneous mixture as an addition agent extend over a wider range of operating conditions than that usually secured by the addition of a single compound.

It is to be understood that other and similar complex organic mixtures, as above described, may be similarly treated with satisfactory results in producing similar addition agents. Likewise catalysts other than aluminum chloride, such as AlBrs, FeCla, ZnClz, etc. which are effective in promoting Friedel-Crafts reaction, may be utilized, although the former is preferred.

The following is an example of the improvement in stability effected by treatment with aluminum chloride: A chlorinated petroleum wax containing approximately 40% chlorine, which had been prepared and purified in the usual way and placed in an oven was maintained at a temperature of 110 to 115 C. At the end of approximately thirty minutes certain of the'constituents of the material began to decompose as evidenced by a noticeable change in color of the composition accompanied by evolution of hydrogen chloride gas. The same material, after being treated with aluminum chloride in accordance with this invention, was subjected to the same test. No decomposition of any of the constituents was noted until after about five and onehalf hours.

Throughout the foregoing description the various compounds referred to have been identified as halogenated compounds. Of the various halogens, chlorine is preferred, principally on account of its low cost and the relative ease by which it may be handled as compared with certain other halogens.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the materials employediwcarrying out the process, provided the ingredient or ingredients stated in any of the following claims or the equivalent of such stated ingredient or ingredients be employed.

I, therefore, particularly point out and distinctly claim as my invention:-

1. A lubricating composition comprising a major proportion of mineral lubricating oil and a minor proportion of stabilized halogenated paramn wax prepared by halogenating paraflin wax until the same contains from about 10% to about 60% halogen, during which halogenation step relatively unstable halogenated constituents are produced in the reaction mixture and then subjecting such reaction mixture to a condensing reaction employing a minor amount of a condensing agent of the type represented by AlCla just sufficient to convert said relatively unstable constituents intostable constituents without substantially modifying the relatively stable constituents of said reaction mixture and then separating the sludge therefrom.

2. A lubricating composition comprising a major proportion of mineral lubricating oil and a minor proportion of stabilized chlorinated paraflin wax prepared by chlorinating paraffin wax until the same contains from about 10% to about 60% chlorine, during which chlorination step relatively unstable chlorinated constituents are produced in the reaction mixture and then subjecting such reaction mixture to a condensing reaction employing a minor amount of a condensing agent of the type represented by AlCla just sufficient to convert said relatively unstable constituents into stable constituents without substantially modifying the relatively stable constituents of said reaction mixture and then separating the sludge therefrom.

3. A lubricating composition comprising a major proportion of mineral lubricating oil and a minor proportion of stabilized halogenated paraflin wax prepared by halogenating paramn wax until the same contains from about 10% to about 60% chlorine, during which halogenation step relatively unstable halogenated constituents are produced in the reaction mixture, preliminarily stabilizing the reaction mixture by means such as air-blowing and then subjecting such reaction mixture to a condensing reaction employ- 5 ing a minor amount of a condensing agent of the type represented by AlClz just suflicient to convert said relatively unstable constituents into stable constituents without substantially modifying the relatively stable constituents of said reaction mixture and then separating the sludge therefrom.

4. A lubricating composition comprising a major proportion of mineral lubricating oil and a minor proportion of stabilized chlorinated par- 15 aflin wax prepared by chlorinating paraflin wax until the same contains from about 10% to about 60% chlorine, during which chlorination step relatively unstable chlorinated constituents are produced in the reaction mixture, preliminarily stabilizing the reaction mixture by means such as air-blowing, and then subjecting such reaction mixture to a condensing reaction employing a minor amount of a condensing agent of the type represented by AlCl: just sufllcient to convert said relatively unstable constituents into stable constituents without substantially modifying the relatively stable constituents of said reaction mixture and then separating the sludge therefrom.

5. A lubricating composition comprising a major proportion of mineral lubricating oil and from 0.10% to 10% of stabilized halogenated paraifin wax prepared by halogenating paraffin wait until the same contains from about 10% to about 35 60% halogen, during which halogenation step\ relatively unstable halogenated constituents are produced in the reaction mixture and then sub- Jecting such reaction mixture to a condensing reaction employing a minor amount of a condens- 40 ing agent of the type represented by AlCla just sumcient to convert said relatively unstable constituents into stable constituents without substantially modifying the relatively stable constituents of said reaction mixture and then 5 separating the sludge therefrom.

6. A lubricating composition comprising a major proportion of mineral lubricating oil and from about 0.25% to. about 3.5% of stabilized halogenated paraflln wax prepared by halogenating paraflin wax until the same contains from about 10% to about 60% halogen, during which halogenation step relatively unstable halogenated constituents are produced in the reaction mixture and then subjecting such reaction mix- 55 ture to a condensing reaction employing a minor amount of a condensing agent of the type represented byAlCla just suflicient to convert said relatively unstable constituents into stable constituents without substantially modifying the rei- 30 atively stable constituents of said reaction mixture and then separating the sludge therefrom.

CARL F. PRU'I'ION. 

